Transparent tooling for uv radiation curable rubber

ABSTRACT

A mold, a molding apparatus, and a method for manufacturing articles or components is used to manufacture an article or component of the article that at least partially comprises an ultraviolet (UV) curable material. The mold and apparatus comprise at least one mold wall formed of a cyclic olefin copolymer, which is in contact with UV radiation curable material and allows the article or component of the article to be exposed to UV radiation for a period of time in order to provide for at least partial cure thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Non-Provisional applicationSer. No. 17/195,122, having the title “TRANSPARENT TOOLING FOR UVRADIATION CURABLE RUBBER,” filed on Mar. 8, 2021, which is a divisionalof U.S. Non-Provisional application Ser. No. 15/959,557, having thetitle “TRANSPARENT TOOLING FOR UV RADIATION CURABLE RUBBER,” filed onApr. 23, 2018, now abandoned, which application claims the benefit ofand priority to U.S. Provisional Application No. 62/547,986, having thetitle “TRANSPARENT TOOLING FOR UV-CURABLE RUBBER,” filed on Aug. 21,2017, U.S. Provisional Application No. 62/488,978, having the title“APPAREL AND SPORTING EQUIPMENT WITH AN UV CURABLE MATERIAL AND METHODOF MANUFACTURING THEREOF,” filed on Apr. 24, 2017, and U.S. ProvisionalApplication No. 62/488,971, having the title “ARTICLE WITH UV CURABLEMATERIAL ADHERED TO TEXTILE AND METHOD OF MAKING THE SAME,” filed onApr. 24, 2017, the contents of which are each incorporated by referencein their entirety.

FIELD

This disclosure relates generally to a mold, a molding apparatus, and amethod for manufacturing articles or components of articles. Morespecifically, the disclosure relates to a mold, a molding apparatus anda method of using an ultraviolet (UV) curable material to form anarticle or a component of an article, including a molded footwear orsporting equipment component.

BACKGROUND

The statements in this section merely provide background informationrelated to the present disclosure and may not constitute prior art.

Conventional molding processes generally involve heating a thermoplasticpolymer resin to a temperature that allows the polymer to flow underpressure, injecting or extruding the polymer into a cavity formed withina mold or die, and allowing the polymer to cool, thereby, forming afinished product that is in the shape or form of the cavity. Materialswhich react to form thermoset polymers may be used in a molding processwithout the need to cool the material to solidify it and form a productthat has the shape of the cavity. When these materials are used, themold is maintained at a temperature and pressure that causes thepolymers to cure or cross-link via a chemical reaction to form athermoset material.

Polymeric materials that are capable of curing upon exposure toultraviolet (UV) radiation are normally not selected for the manufactureof articles or components of articles that are relatively thick in atleast one dimension and/or exhibit a complex geometry. Since UV curableresins only cure in regions that are exposed to a threshold level of UVradiation, a thick component or one having a complex geometry may sufferfrom one or more regions remaining uncured. Thus, UV curable resins arenormally used only to form thin layers, such as those found in theapplication of coatings or adhesives.

The molds used in conventional molding processes are usually expensiveto build and/or replace. These molds are often made of steel in order towithstand the high temperature and/or pressure requirements of themolding process. The cost of these molds may further be increased whenthe surface of the metal that forms the cavity of the mold needs to bepolished or textured.

DRAWINGS

In order that the disclosure may be well understood, there will now bedescribed various forms thereof, given by way of example, referencebeing made to the accompanying drawings, in which:

FIG. 1A is perspective top-down view of a mold apparatus formedaccording to the teachings of the present disclosure;

FIG. 1B is a perspective view of the bottom portion of the mold shown inFIG. 1A;

FIG. 10 is a perspective view of the interior of the top portion of themold shown in FIG. 1A;

FIG. 2A is a flow chart of a method of forming a mold according to theteachings of the present disclosure;

FIG. 2B is a flow chart of a method of forming an article or a componentof an article using the mold of FIG. 2A;

FIGS. 3 (A-C) are perspective views of articles or components ofarticles formed according to the method of FIG. 2B;

FIGS. 4 (A-B) are perspective views of another article or a component ofan article formed according to the method of FIG. 2B;

FIG. 5 is a flow chart of a method of forming an article of footwearaccording to the teachings of the present disclosure;

FIG. 6 is a perspective view of a mold apparatus formed according to theteachings of the present disclosure that may be used to manufacture anarticle from a UV radiation curable material; and

FIGS. 7 (A-E) is a perspective view of another mold apparatus formedaccording to the teachings of the present disclosure that may be used tomanufacture a component of an article from a UV radiation curablematerial.

The drawings described herein are for illustration purposes only and arenot intended to limit the scope of the present disclosure in any way.

DETAILED DESCRIPTION

The use of ultraviolet (UV) radiation curable materials in forming or atleast partially forming an article or a component of an article offersmultiple benefits to a manufacturing operation. More specifically, theuse of such materials may increase productivity, lower costs associatedwith the fabrication of a mold, lower energy costs, and induce less partshrinkage due to low curing temperatures and faster cure times. However,in order to process such materials, the manufacturing operation needs toinclude equipment and processes that allow the UV radiation curablematerials to be exposed to ultraviolet (UV) radiation for a duration oftime that is necessary to at least partially cure the material. Thepresent disclosure generally relates to a mold, a molding apparatus, anda method of using UV curable materials to form an article or a componentof an article, including a molded footwear or sporting equipmentcomponent.

According to one aspect of the present disclosure, a mold for forming amolded article is provided that comprises a mold wall formed of a cyclicolefin copolymer. The mold also includes a molding surface for contactwith an article-forming material in order to form the molded article.

According to another aspect of the present disclosure, a method formaking a mold used to form a molded article is described. This methodincludes forming a mold wall comprising a cyclic olefin copolymer andhaving a molding surface for contact with an article-forming materialfor forming the molded article. When necessary or desirable the step offorming the mold wall may comprise introducing a molten cyclic olefincopolymer to a master mold and solidifying the molten cyclic olefincopolymer in the master mold to form the mold wall.

A method for forming a molded article may also comprise the followingsteps according to another method of the present disclosure. Anarticle-forming material is introduced in to a mold that includes a moldwall comprising a cyclic olefin copolymer. The article-forming materialmakes contact with a molding surface of the mold wall in order to formthe molded article.

According to yet another aspect of the present disclosure, an apparatusfor forming a molded article is provided. This apparatus includes a moldhaving a mold wall that comprises a cyclic olefin copolymer and that issubstantially transparent to UV light. The mold wall has a moldingsurface for contacting an article-forming material. An UV light sourceis disposed adjacent to the mold wall on a side opposite the moldingsurface and configured to generate UV light for transmission through themold wall to the molding surface for exposing the article-formingmaterial to the UV light.

Thus, the present disclosure generally provides a mold, a moldingapparatus, and a method for manufacturing articles or components ofarticles. The article or component of the article at least partiallycomprises an UV radiation curable material. Thus, the mold, apparatus,and method of molding the article or component of the article mayinclude exposure of the UV radiation curable material to UV radiationfor a period of time that allows at least partial cure thereof. Furtherareas of applicability will become apparent from the descriptionprovided herein.

The following description and specific examples are merely exemplary innature and is in no way intended to limit the present disclosure or itsapplication or uses. For example, the molded component comprising an UVradiation curable material made and used according to the teachingscontained herein is described throughout the present disclosure inconjunction with footwear in order to more fully illustrate thecomposition and the use thereof. The incorporation and use of such amolded UV radiation curable component in other applications, includingapparel such as garments, sporting equipment, or the like, as well ascomponents thereof, are contemplated to be within the scope of thepresent disclosure. It should be understood that throughout thedescription, corresponding reference numerals indicate like orcorresponding parts and features.

Referring to FIGS. 1A-1C, the mold 1 generally comprises a cavity 5formed in a bulk material 10. At least a portion of the surface ofcavity 5 within the mold 1 is formed of a mold wall 15 comprised of oneor more cyclic olefin copolymers as further described herein. Thesurface of this mold wall 15 (i.e., a molding surface) is in contact,either directly or indirectly, with the UV radiation curable material orresin that is placed within the mold 1 to form an article or a moldedcomponent of the article. Alternatively, the molding surface or thesurface of the mold wall 15 is in direct contact with the UV radiationcurable material used to form the article or the molded component of thearticle. The molding surface may exhibit a surface energy that is in therange of about 15 dynes/cm to about 35 dynes/cm at 20° C. Alternatively,the surface energy of the molding surface is between about 20 dynes/cmto about 30 dynes/cm. The mold may be used to form a molded footwearcomponent, a molded apparel component, or a molded sporting equipmentcomponent. Alternatively, the mold is used to form a molded footwearcomponent.

For the purpose of this disclosure the terms “about” and “substantially”are used herein with respect to measurable values and ranges due toexpected variations known to those skilled in the art (e.g., limitationsand variability in measurements).

For the purpose of this disclosure any range in parameters that isstated herein as being “between [a 1^(st) number] and [a 2^(nd) number]”or “between [a 1^(st) number] to [a 2^(nd) number]” is intended to beinclusive of the recited numbers. In other words the ranges are meant tobe interpreted similarly as to a range that is specified as being “from[a 1^(st) number] to [a 2^(nd) number]”.

The cyclic olefin copolymers comprise one or more amorphous, transparentcopolymers based on cyclic olefins and linear olefins. The cyclic olefincopolymers may include copolymers that have the general formula shown inEquation 1, where x and y represent integers that defines the ratio oflinear to cyclic segments (e.g., ratio of x to y) in the cyclic olefincopolymer. Alternatively, the cyclic olefin copolymer may comprise acopolymer of polyethylene and norbornene.

The cyclic olefin copolymers provide the benefits of being at leastpartially transparent to UV radiation, low density, low birefringence,low water absorption, high heat deflection temperature, and goodprocessability (e.g., flowability), as well as high strength, hardness,and rigidity. Alternatively, the cyclic olefin copolymer used to formthe mold wall 15 is substantially transparent to UV light or radiationand allows the UV radiation to be transmitted through the mold wall 15to the molding surface and to the UV radiation curable material used toform the article or the molded component of the article. Severalspecific examples of cyclic olefin copolymers include, withoutlimitation, materials that are commercially available under thetradenames TOPAS®, including TOPAS® 6017 and TOPAS® 6015, (TopasAdvanced Polymers, Florence, Ky., USA) and APEL™ (Mitsui Chemicals Inc.,Tokyo, Japan).

The cyclic olefin copolymers exhibit transparency on the order of about80% to 100%, alternatively, about 90% for light that is in the nearultraviolet region (i.e., ˜300 nm to ˜400 nm wavelength) and visibleregion (i.e., ˜400 nm to ˜700 nm wavelength). The cyclic olefincopolymers may further exhibit transparency of light within a wavelengthranging from about 250 nm to less than 300 nm that is on the order ofabout 10% to about 85%. In some examples, the cyclic olefin copolymersexhibit greater than about 20% light transmittance.

In order to more easily process the UV radiation curable material, aswell as provide a buffer between processing and deflection, a moldcomprising a cyclic olefin copolymer that exhibits a high deflectiontemperature (HDT) may be desirable. Typically, a cyclic olefin copolymerwith a higher cyclic olefin component (i.e., segment y) will exhibit ahigher heat resistance. In this respect, the cyclic olefin copolymer mayexhibit a heat deflection temperature (HDT) at 0.46 MPa of at least 140°C. as characterized by HDT testing in accordance with the ISO 75-1 TestStandard. Alternatively, the HDT of the cyclic olefin copolymers rangesfrom about 165° C. to about 200° C. Several specific examples ofcommercially available cyclic olefin copolymers that have an HDT in thisrange include, without limitation, Topas® 6015 and 6017 (Topas AdvancedPolymers Inc.) with an HDT of 150° C. and 170° C., respectively.

The cyclic olefin copolymer may be pre-compounded as sheets or be in theform of a pelletized material, flakes, strips, or any other form asdesired or necessary to meet application requirements. The cyclic olefincopolymer may be milled to provide a thinner thickness and/or to reducethe presence of air voids. When desirable, the cyclic olefin copolymermay be dried to remove any residual moisture prior to be formed into amold. Although optional, pre-drying the cyclic olefin polymer may reducethe amount of moisture splay present in the mold wall formed therefrom,resulting in an increased level of optical transparency. Any knownmethod of pre-drying the cyclic olefin copolymer may be utilized. Thesemethods may include but not be limited to drying the cyclic olefincopolymer in a dehumidifying oven at 80° C. or higher for apredetermined amount of time, such as for example, a period greater thanabout 1 hour; alternatively, greater than about 2.5 hours;alternatively, greater than about 4 hours.

Referring once again to FIGS. 1A-1C, the bulk material 10 of the mold 1may be comprised of a metal or metal alloy, a thermally stable polymermaterial, a ceramic material, or a mixture thereof. The mold 1 may beused, without limitation, in a compression molding operation or aninjection molding process. Optionally, the mold 1 may comprisemechanical features and connections that allow one or more moldingsurfaces 15 located in the cavity 5 to be heated and/or cooled.

The bulk material 10 portions of the mold 1 may be manufactured fromplanar sheet materials that have a constant thickness. When desirablethis sheet material may include a plurality of UV radiation deflectingparticles within the bulk material 10 or positioned on the surface ofthe bulk material 10, such as incorporated within a coating appliedthereto. For the purpose of this disclosure, a UV radiation deflectingparticle means any particle capable of diverting the direction of thetransmitted UV radiation by scattering and/or reflection thereof.

The bulk material 10 may be transformed into the desired shape of thearticle or component of the article by any known process, including butnot limited to, machining, thermoforming and/or assembling, such thatthe interior contour of the cavity 5 represents the negative or positiveform of the article or component of the article that is to be shapedwithin the mold 1.

The wall thickness of the bulk material, as well as thickness of themold wall that comprises the UV transparent material (i.e., the cyclicolefin copolymer) can vary from about 0.5 millimeters (mm) to about 75mm, allowing for the manufacture of flexible or rigid molds.Alternatively, the wall thickness of the bulk material and/or UVtransparent mold wall is within the range of about 1.0 mm to about 50mm; alternatively, within the range of about 1.5 mm to about 30 mm;alternatively, within the range of about 2.0 mm to about 15 mm;alternatively within the range of about 2.0 mm to about 10 mm.

According to another aspect of the present disclosure the inner volumeof the cavity allows for the formation of a molded component having athickness that is greater than about 0.05 millimeters (mm);alternatively, with the range of about 0.05 mm to about 1.0 cm;alternatively, within the range of about 1.0 mm to about 5.0 mm. Thethickness of the molded article or molded component of the article maybe variable over the length and/or width of the article or the moldedcomponent. The thickness of the bulk material 10 and the UV transparentmold wall 15 that are within the indicated range provide a mold 1 thatis durable for use through multiple molding cycles.

In particular examples, the UV transparent mold wall, the moldingsurface, or both the UV transparent mold wall and the molding surfaceexhibits transparency on the order of about 80% to 100%, alternatively,about 90% for light that is in the near ultraviolet region (i.e., ˜300nm to ˜400 nm wavelength) and visible region (i.e., ˜400 nm to ˜700 nmwavelength). The UV transparent mold wall, the molding surface, or boththe UV transparent mold wall and the molding surface may further exhibittransparency of light having a wavelength ranging from about 250 nm toless than 300 nm that is on the order of about 10% to about 85%. In someexamples, the mold wall, the molding surface, or both the UV transparentmold wall and the molding surface exhibits greater than about 20% lighttransmittance.

The mold 1 may comprise more than one part or die portion 1 a (FIG. 1B),1 b (FIG. 10 ) that fit together to form the cavity 5 bordered by themolding surface(s) 15. The different parts 1 a, 1 b of the mold may bedesigned to be held together using a variety of different fasteners,including without limitation, the mating combination of pins 11 andsockets 13. In other words, the mold wall 15 may form at least part of afirst die portion 1 a, and the mold 1 further comprises a second dieportion 1 b, wherein the first and second die portions 1 a, 1 b areconfigured to move relative to each other between an opened position anda closed position, and wherein the first and second die portions 1 a, 1b in the closed position defines a cavity 5 for molding the UV radiationcurable material that forms the article or the molded component of thearticle. When the mold 1 is used in a compression molding process, thefirst and second die portions 1 a, 1 b may be configured for compressionmolding the UV radiation curable material to form the molded article orthe molded component of the article.

Referring again to FIG. 1A, the mold 1 may form part of a moldingapparatus 20, which also comprises an UV light source 25. The UV lightsource 25 and the mold 1 may be separable from each other or inherentlycombined to form the molding apparatus 20. In other words, the apparatus20 may comprise a mold 1 made of only one or of a plurality of mold ordie portions 1 a, 1 b that can be fitted together to form the mold 1 andseparated from each other to release a manufactured product from themold 1. Alternatively, the apparatus 20 may further comprise a conveyorsystem or similar mechanism to move the mold 1 or the UV light source 25into a position in which the UV radiation arising from the light source25 is aligned with the UV transparent portion of the mold wall 15. Onespecific example, among many examples, of an apparatus 20 that comprisesa conveyor system capable of moving a separable mold past an UV lightsource is the LC6B/LC6B-2 UV curing unit available from HeraeusNoblelight America LLC (Gaithersburg, Md.).

The UV light source 25 generates UV radiation of which at least aportion thereof is transmitted through the molding surface 15 to thearticle-forming or UV radiation curable material placed within thecavity 5 and in contact with molding surface 15. In other words, theapparatus 20 comprises a mold 1 having a mold wall 15 that comprises acyclic olefin copolymer and that is substantially transparent toultraviolet (UV) light, wherein the mold wall 15 has a molding surfacefor contacting an article-forming material; and an UV light source 25disposed adjacent to the mold wall 15 on a side opposite the moldingsurface and configured to generate UV radiation for transmission throughthe mold wall 15 to the molding surface for exposing the article-formingmaterial to the UV light.

The UV light source may include any type of UV light that transmits UVradiation in a wavelength to which the cyclic olefin copolymer used inthe mold wall is at least partially transparent (e.g., can be at leastpartially transmitted there through). Several examples of UV lightsources, include but are not limited to, xenon lamps, mercury lamps,black-light lamps, excimer lasers and UV-LED lamps. Alternatively, theUV light source is an UV-LED lamp; a low, medium, or high pressuremercury vapor lamp; a xenon lamp; a quartz halogen lamp; or a laseroperating in the short wavelength portion of the spectra. Several morespecific examples of UV light sources include, but are not limited to,short-wave UV lamps, gas-discharge lamps, ultraviolet LEDs, UV lasers,tunable vacuum ultraviolet (VUV) obtained from sum and differencefrequency mixing, or plasma and synchrotron sources of extreme UVradiation. When desirable more than one light source may be used witheach light source being individually selected. When desirable ordetermined necessary, the irradiation intensity of the UV light at thepreviously defined wavelength to which the UV radiation curable materialis exposed may be within the range of about 0.5 W/cm² to about 5 W/cm²;alternatively, about 1.0 W/cm² to about 4.0 W/cm²; alternatively, withinthe range of 1.5 W/cm² to 4.0 W/cm².

Referring now to FIG. 2A, a method 100 of making a mold for use informing a molded article or component of an article from a UV radiationcurable material is provided. This method 100 comprises forming 110 amold wall that comprises a cyclic olefin copolymer and has a moldingsurface for making contact with the article-forming material (i.e., theUV radiation curable material). The mold wall may be formed byintroducing 115 molten cyclic olefin copolymer to a master mold andallowing the molten copolymer to solidify 120 in the master mold,thereby, forming the mold wall. The master mold includes a cavityencompassed by molding surfaces that is the negative or positive imageof the shape desired for the mold that will be used to form a moldedarticle or component from the article-forming (i.e., UV radiationcurable) material.

The introduction 115 of the molten cyclic olefin copolymer into themaster mold may be, without limitation, part of an injection moldingprocess 125 or an extrusion process. The cyclic olefin copolymer isheated to a temperature that ranges from about 260° C. to about 320° C.;alternatively, ranging from about 260° C. to about 310° C.;alternatively, from about 270° C. to about 320° C., prior to beingintroduced 115 into the master mold. The molten cyclic olefin copolymeris solidified 120 in the master mold, which is maintained at a lowertemperature. The temperature of the master mold may be about 160° C. orless; alternatively, in the range from about 120° C. to about 160° C.

Referring now to FIG. 2B, a method 150 of forming a molded article orcomponent of an article is also provided in which the article-forming(i.e., UV radiation curable) material is introduced 155 in the molddescribed above that comprises a mold wall formed at least partially ofthe cyclic olefin copolymer. The article-forming material contacts 160the molding surface of the surface of the mold wall in order to form themolded article or component. When desirable, the cyclic olefin copolymermay comprise a copolymer of polyethylene and norbornene.

When desirable, various precautions or safeguards may be undertaken byone skilled in the art in order to protect 153 at least a portion of theUV-curable material from being exposed to UV radiation during one ormore steps of the method. Such precautions or safeguards may include,but not be limited to, masking a portion of the UV radiation curablematerial or the surface upon which the material is in contact, as wellas maintaining the UV radiation curable material in an environment thatis absent any UV light or visible light or both.

The mold wall is at least partially transparent; alternatively,substantially transparent to UV light or radiation. In this sense, themethod may further comprise transmitting 165 the UV light through themold wall to the molding surface for exposing the article-formingmaterial to the UV light. The UV radiation curable material is cured 170in response to being exposed to the UV radiation. The UV radiationcurable material is exposed to the UV radiation in an amount and for aduration that is sufficient to partially cure or fully cure the UVradiation curable material.

For the purpose of this disclosure, the term “partially cured” isintended to denote the occurrence of at least about 1%, alternatively,at least about 5% of the total polymerization required to achieve asubstantially full cure. The term “fully cured” is intended to mean asubstantially full cure in which the degree of curing is such that thephysical properties of the UV radiation curable material does notnoticeably change upon further exposure to additional UV radiation.

The UV radiation curable material generally comprises one or morephotopolymers or light-activated resins that will undergo across-linking reaction upon exposure to UV radiation. The UV radiationcurable material may comprise a mixture of various multifunctionalmonomers, oligomers, and/or low molecular weight polymers or copolymers,along with one or more photoinitiator(s) that can undergo polymerizationin the presence of UV radiation. Upon exposure to UV radiation, thephotoinitiator decomposes into a reactive species that activatespolymerization of specific functional groups that are present in themultifunctional oligomers, monomers, or polymers.

As used herein, the term “polymer” refers to a molecule havingpolymerized units of one or more species of monomer. The term “polymer”is understood to include both homopolymers and copolymers. The term“copolymer” refers to a polymer having polymerized units of two or morespecies of monomers, and is understood to include terpolymers. As usedherein, reference to “a” polymer or other chemical compound refers oneor more molecules of the polymer or chemical compound, rather than beinglimited to a single molecule of the polymer or chemical compound.Furthermore, the one or more molecules may or may not be identical, solong as they fall under the category of the chemical compound. Thus, forexample, “a” polyurethane is interpreted to include one or more polymermolecules of the polyurethane, where the polymer molecules may or maynot be identical (e.g., different molecular weights).

The end result of curing a light-activated resin in this manner is theformation of a thermoset or cross-linked polymer network. Thus, the UVradiation curable material may be described as being an UV radiationcurable elastomer. Alternatively, the UV radiation curable material maycomprise an UV radiation curable rubber. The UV radiation curablematerial may comprise one or more thermoset polymers, thermoplasticpolymers, or combinations thereof. When desirable, the one or morethermoplastic polymers may be one or more thermoplastic polyurethanes(TPU).

Several specific examples of various monomers that may be used in the UVradiation curable material include, but are not limited to, styrene andstyrenic compounds, vinyl compounds, vinyl ethers, N-vinyl carbazoles,lactones, lactams, cyclic ethers, cyclic acetals, and cyclic siloxanes.Several specific examples of oligomers and low molecular weight polymersor copolymers that may be incorporated into the UV radiation curablematerial include, without limitation, vinyl butadiene, epoxides,urethanes, polyethers, or polyesters, each of which provide specificproperties to the resulting material. Each of these oligomers orpolymers may be functionalized using an acrylate. Alternatively, the UVradiation curable material may include a mixture of urethane andacrylate oligomers or a copolymer thereof.

Photoinitiation may occur via a free radical mechanism, an ionicmechanism, or a combination thereof. Under an ionic mechanism, thepolymerizable oligomers, monomers, or polymers are doped with eitheranionic or cationic photoinitiators. Several examples of suchphotoinitiators, include without limitation, onium salts, organometalliccompounds, and pyridinium salts. In the free radical mechanism, thephotoinitiators generate free-radicals by the abstraction of a hydrogenatom from a donor or co-initiator compound (i.e., a 2-component system),or by the cleavage of a molecule (i.e., a 1-component system). Severalspecific examples of abstraction type photoinitiators, include but arenot limited to, benzophenone, xanthones, and quinones with common donorcompounds being aliphatic amines. Several specific examples ofcleavage-type photoinitiators include, without limitation, benzoinethers, acetophenones, benzoyl oximes, and acylphosphines. Photocurablematerials that form through the free-radical mechanism undergochain-growth polymerization, which includes three basic steps:initiation, chain propagation, and chain termination. Alternatively, thephotoinitiators are independently selected and may include phosphineoxides, benzophenones, a-hydroxy-alkyl aryl ketones, thioxanthones,anthraquinones, acetophenones, benzoins and benzoin ethers, ketals,imidazoles, phenylglyoxylic acids, peroxides, and sulfur-containingcompounds.

The amount of photoinitiators present in the UV radiation curablematerial is determined by the effective amount necessary to inducecrosslinking of the UV radiation curable material. This amount may rangefrom about 0.05 weight percent (wt. %) to about 5 wt. %, alternatively,from about 0.1 wt. % to about 2 wt. %, and alternatively, from about 0.2wt. % to about 1 wt. % based on the weight of the UV radiation curablematerial. A single type of photoinitiator or a mixture of differentphotoinitiators may be used.

For the purpose of this disclosure, the term “weight” refers to a massvalue, such as having the units of grams, kilograms, and the like.Further, the recitations of numerical ranges by endpoints include theendpoints and all numbers within that numerical range. For example, aconcentration ranging from 40% by weight to 60% by weight includesconcentrations of 40% by weight, 60% by weight, and all concentrationsthere between (e.g., 40.1%, 41%, 45%, 50%, 52.5%, 55%, 59%, etc.).

According to another aspect of the present disclosure, the UV radiationcurable material may comprise, consist of, or consist essentially of amillable polyurethane gum that includes ethylenic unsaturation, one ormore photoinitiators, and at least one additional crosslinking additivethat comprises two or more ethylenically unsaturated groups. Themillable polyurethanes may be prepared by the reaction of a di- orpolyisocyanate with bis(hydroxyl)-functional compounds, at least one ofwhich contains ethylenic unsaturation. Alternatively, unsaturatedpolyester polyols may be used, alone or in combination with otherisocyanate-reactive components, such as polyoxyalkylene glycols and/ordiols capable of providing pendent ethylenic unsaturation. A commercialexample of such a UV radiation curable material is Millathane® UV (TSEIndustries Inc., Clearwater, Fla.). A further description of such UVradiation curable materials is provided in U.S. Publication No.2016/0362552, the entire content of which is hereby incorporated byreference.

For the purpose of this disclosure, the terms “at least one” and “one ormore of” an element are used interchangeably and may have the samemeaning. These terms, which refer to the inclusion of a single elementor a plurality of the elements, may also be represented by the suffix“(s)” at the end of the element. For example, “at least onepolyurethane”, “one or more polyurethanes”, and “polyurethane(s)” may beused interchangeably and are intended to have the same meaning.

The additional crosslinking additive present in the curable polyurethanecomposition may include any low molecular weight compounds that containtwo or more ethylenically unsaturated groups. These unsaturated groupsmay include, without limitation, glycerol diallyl ether, 1,6-hexanedioldi(meth)acrylate, triallylisocyanurate, trimethylolpropanedi(meth)acrylate, trimethylolpropane tri(meth)acrylate, glyceroldi(meth)acrylate, glycerol tri(meth)acrylate, propoxylated glyceroltriacrylate, 1,2-divinyltetramethyldisiloxane, divinylbenzene, and thelike. The molecular weight of this additional crosslinking additive maybe less than about 2000 Da, alternatively less than about 1000 Da,alternatively less than about 500 Da. The concentration of thecrosslinking additive in the UV radiation curable material is selectedbased upon the amount of ethylenic unsaturated groups that are desired.The concentration of this additive may range from about 0.01 wt. % toabout 15 wt. %, alternatively, from about 1 wt. % to about 12 wt. %, andalternatively, from about 5 wt. % to about 10 wt. % based on the overallweight of the UV radiation curable material.

When desirable, the UV radiation curable material may optionallycomprise one or more additional processing aids, including withoutlimitation, plasticizers, mold release agents, lubricants, antioxidants,flame retardants, dyes, pigments, reinforcing and non-reinforcingfillers, fiber reinforcements, and light stabilizers or UV absorbers.When an UV absorber is incorporated into the UV radiation curablematerial in order to enhance the environmental stability thereof, it maybe necessary or desirable to use a more powerful UV light source toachieve full cure of the material, or use an UV light source having anoutput wavelength that is in a range within the UV spectrum at which theUV absorber exhibits a reduced level of absorbance.

The reinforcing fillers that may optionally be incorporated into the UVradiation curable material may be organic, i.e. polymeric, or inorganicin nature. These fillers may exhibit a mean, weight average particlesizes that is ≤1 □m, alternatively, in the range between about 20nanometers (nm) to about 500 nm. Several specific examples ofreinforcing fillers include, but are not limited to, pyrogenic (i.e.,fumed) metal oxides, such as alumina, titania, ceria, silica, and thelike; colloidal metal oxides, such as colloidal alumina or silica;carbon black and acetylene black; metal hydroxides, such as aluminumhydroxide; glass or polymer microspheres; or limestone, talc, clay, andthe like. The amount of filler present in the UV radiation curablematerial is selected based upon the requirements associated with aparticular end use. Typically, the amount of reinforcing filler presentin the UV radiation curable material ranges from 0 wt. % to about 20 wt.% based on the total weight of the UV radiation curable material.Fillers having the same chemical composition may be considered to benon-reinforcing fillers when their mean, weight average particle size isgreater than 1 □m, alternatively, in the range of about 2 mm to about500 mm.

The UV radiation curable material may be cured by irradiation with UVlight transmitting a wavelength that is the same as the excitationwavelength exhibited by the photoinitiator present. The duration in timethat the UV radiation curable material is irradiated with UV radiationis variable and based upon the nature and type of reactive oligomers,monomers, or polymers present in the UV radiation curable material, aswell as type and concentration of the crosslinking additives,photoinitiators, and fillers, as well as the type and power associatedwith the available UV light source. The duration of UV exposure mayrange less than a second to several hours; alternatively, the exposuretime is between about 1 second and about 1 hour; alternatively, betweenabout 5 seconds and 5 minutes. The UV radiation curable material may beirradiated at ambient or room temperature within the confines of amolding operation or at a temperature associated with the componentformed in a molding or extrusion process. When desirable the molded partmay be subjected to a cooling step prior to irradiation with UV light.Although, no thermal cure is necessary, a dual cure system may be usedwhen desirable.

According to another aspect of the present disclosure, the article orcomponent of the article formed from the UV radiation curable materialaccording to the teachings of the present disclosure may be, withoutlimitation, a garment, sporting equipment, or footwear. Alternatively,the article is component of a garment, sporting equipment, or footwear.For example, referring to FIGS. 3A and 3B, the component of sportingequipment may be a part or section 175 of a backpack 180 or a hat 190,including but not limited to a logo. Similarly, as shown in FIG. 3C, thecomponent of a garment may be a part or section 175 of a shirt 195. InFIGS. 4A and 4B, the component of the article of footwear 200 may be anoutsole 220, for example, or a logo or other component 240. As usedherein, the terms “article of footwear” and “footwear” are intended tobe used interchangeably to refer to the same article. Typically, theterm “article of footwear” will be used in a first instance, and theterm “footwear” may be subsequently used to refer to the same articlefor ease of readability.

The article of footwear or shoe of the present disclosure may bedesigned for a variety of uses, such as sporting, athletic, military,work-related, recreational, or casual use. The article of footwear maybe used outdoors on paved or unpaved surfaces (in part or in whole),such as on a ground surface including one or more of grass, turf,gravel, sand, dirt, clay, mud, and the like, intended for theperformance of an athletic competition or as a general outdoor surface.The article of footwear may also be desirably used with indooractivities, such as indoor sports, shopping, and everyday work.

Referring now to FIGS. 4A and 4B, the footwear 200 or shoe 200 maycomprise, consist of, or consist essentially of an upper 210 and anoutsole 220 having a predetermined shape. The outsole 220 is in contactwith and attached to the upper 210. At least part of the upper 210and/or the outsole 220 comprises the UV radiation curable material asdescribed above and further defined herein in an uncured or partiallycured state.

Still referring to FIGS. 4A and 4B, the outsole 220 refers to the verybottom of the shoe that is in direct contact with the ground. Theoutsole 220 may be relatively smooth or include one or more tractionelements 225. These traction elements 225 may provide enhanced traction,as well as provide support or flexibility to the outsole and/or providean aesthetic design or look to the shoe. The traction elements 225 mayinclude, but are not limited to a tread pattern, as well cleats, studs,spikes, or similar elements configured to enhance traction for a wearerduring cutting, turning, stopping, accelerating, and backward movement.

Since the outsole 220 is the outer most sole of the shoe, it is directlyexposed to abrasion and wear. Similarly, portions of the upper 210 aredirectly exposed to abrasion and wear. Various portions of the outsole220 may be constructed with different thickness and exhibit differentdegrees of flexibility. The materials that comprise the outsole 220should provide some degree of waterproofing, durability, and possess acoefficient of friction that is high enough to prevent slipping. In somecases two or more materials of different densities can be incorporatedinto the outsole 220 to give a hard wearing outer surface and a softer,more flexible midsole 230 for greater comfort. The upper 210 and/or theoutsole 220 may be a single layer or may contain multiple layers of thesame or similar material, provided at least a portion of the upper 210,at least a portion of the outsole 220, or portions of both the upper 210and the outsole 220 comprise an UV radiation curable material.Alternatively, substantially all of the outsole comprises an UVradiation curable material.

The outsole 220 may be directly or otherwise operably secured to theupper 210 using any suitable mechanism or method. As used herein, theterms “operably secured to”, such as for an outsole that is operablysecured to an upper, refers collectively to direct connections, indirectconnections, integral formations, and combinations thereof. Forinstance, for an outsole that is operably secured to an upper, theoutsole can be directly connected to the upper (e.g., adhered directlythereto or glued with a cement or an adhesive), can be integrally formedwith the upper (e.g., as a unitary component), and combinations thereof.

Still referring to FIGS. 4A and 4B, the upper 210 of the footwear 200has a body which may be fabricated from materials known in the art formaking articles of footwear, and is configured to receive a user's foot.The upper 210 of a shoe consists of all components of the shoe above theoutsole 220. The different components of the upper 210 may include a toebox, heal counter, and an Achilles notch, to name a few. Thesecomponents are attached by stitches or adhesives to become a single unitto which the outsole is attached.

The upper 210 or components of the upper 210 may comprise a soft bodymade up of one or more lightweight materials. When desirable, the UVradiation curable material may be used to form a portion of the upperand/or a portion of a component of the upper. Such components of theupper may include, but not be limited to, a toe cap, a heel counter, arand, or an eyelet stay, to name a few.

The materials used in the upper 210 provide stability, comfort, and asecure fit. For example, the upper may be made from or include one ormore components made from one or more of natural or synthetic leather, atextile or both. The textile may include; a knit, braided, woven, ornonwoven textile made in whole or in part of a natural fiber; a knit,braided, woven or non-woven textile made in whole or in part of asynthetic polymer, a film of a synthetic polymer, etc.; and combinationsthereof. The textile may include one or more natural or synthetic fibersor yarns. The synthetic yarns may comprise, consist of, or consistessentially of thermoplastic polyurethane (TPU), polyamide (e.g.,Nylon®, etc.), polyester (e.g., polyethylene terephthalate or PET),polyolefin, or a mixture thereof.

The upper 210 and components of the upper 110 may be manufacturedaccording to conventional techniques (e.g., molding, extrusion,thermoforming, stitching, knitting, etc.). While illustrated in FIGS. 4Aand 4B as a generic design, the upper 310 may alternatively have anydesired aesthetic design, functional design, brand designators, or thelike.

Still referring to FIGS. 4A and 4B, the upper 210 may further compriselaces, flaps, straps, or other securing or foot engagement structures213 used to securely hold the shoe 200 to a wearer's foot. A tonguemember, bootie, or other similar type structure may be provided in ornear the shoe instep area in order to increase comfort and/or tomoderate the pressure or feel applied to the wearer's foot by any footengagement structures 213.

When desirable, at least a portion of the upper 210 of the article offootwear, and in some embodiments substantially the entirety of theupper, may be formed of a knitted component. According to one aspect ofthe present disclosure, one or more pieces may be cut from a warp knittextile or a weft knit textile and assembled to form a portion of theupper 210. According to another aspect of the present disclosure, theupper may be formed by knitting to shape one or more large portionsusing, for example, flat knitting or circular knitting techniques. Theupper may be formed by stitching together areas of the flat or circularknit, such as stitching together edges of a flat knit component, orstitching together the toe region of a circular knit component. Theknitted component may additionally or alternatively form another elementof the article of footwear 210 such as the insole, for example.

The knitted component may have a first side forming an inner surface ofthe upper 210 (e.g., facing the void of the article of footwear 200) anda second side forming an outer surface of the upper 210. An upper 210including the knitted component may substantially surround the void soas to substantially encompass the foot of a person when the article offootwear is in use. The first side and the second side of the knittedcomponent may exhibit different characteristics (e.g., the first sidemay provide abrasion resistance and comfort while the second side may berelatively rigid and provide water resistance). The knitted componentmay be formed as an integral one-piece element during a knittingprocess, such as a weft knitting process (e.g., with a flat knittingmachine or circular knitting machine), a warp knitting process, or anyother suitable knitting process. That is, the knitting process maysubstantially form the knit structure of the knitted component withoutthe need for significant post-knitting processes or steps.Alternatively, two or more portions of the knitted component may beformed separately and then attached. In some embodiments, the knittedcomponent may be shaped after the knitting process to form and retainthe desired shape of the upper (for example, by steaming the knittedcomponent or fusing portions of the knitted component while the knittedcomponent is on a foot-shaped last). The shaping process may includeattaching the knitted component to another component (e.g., a strobel,etc.) and/or attaching one portion of the knitted component to anotherportion of the knitted component at a seam by sewing, by using anadhesive including a heat-activated adhesive, or by another suitableattachment process.

Forming the upper 210 with the knitted component may provide the upper210 with advantageous characteristics including, but not limited to, aparticular degree of elasticity (for example, as expressed in terms ofYoung's modulus), breathability, bendability, strength, moistureabsorption, weight, and abrasion resistance. These characteristics maybe accomplished by selecting a particular single layer or multi-layerknit structure (e.g., a ribbed knit structure, a single jersey knitstructure, or a double jersey knit structure), by varying the size andtension of the knit structure, by using one or more yarns ormonofilaments formed of a particular material (e.g., a polyestermaterial or an elastic material, such as spandex), by selecting yarns ofa particular size (e.g., denier), or a combination thereof. The knittedcomponent may also provide desirable aesthetic characteristics byincorporating yarns having different colors or other visual propertiesarranged in a particular pattern. The yarns and/or the knit structure ofthe knitted component may be varied at different locations such that theknitted component has two or more portions with differentcharacteristics (e.g., a portion forming the throat area of the uppermay be relatively elastic while another portion may be relativelyinelastic). Yarns may also be coated with different materials, such asthermoplastic materials that have a lower melting point than thethermoplastic material that forms the core of the yarn.

In some embodiments, the knitted component may incorporate one or morematerials with properties that change in response to a stimulus (e.g.,temperature, moisture, electrical current, magnetic field, or light).For example, the knitted component may include yarns formed of athermoplastic polymer material (e.g., polyurethanes, polyamides,polyolefins, and nylons) that transitions from a solid state to asoftened or liquid state when subjected to certain temperatures at orabove its melting point and then transitions back to the solid statewhen cooled. The thermoplastic polymer material may provide the abilityto heat and then cool a portion of the knitted component thereby formingan area of bonded or continuous material that exhibits certainadvantageous properties including a relatively high degree of rigidity,strength, and water resistance, for example.

In some embodiments, the knitted component may include one or more yarnsor strands that are at least partially inlaid or otherwise insertedwithin the knit structure of the knitted component during or after theknitting process, herein referred to as “tensile strands.” The tensilestrands may be substantially inelastic so as to have a substantiallyfixed length. The tensile strands may extend through a plurality ofcourses of the knitted component or through a passage within the knittedcomponent and may limit the stretch of the knitted component in at leastone direction. For example, the tensile strands may extend approximatelyfrom a bite-line of the upper to a throat area of the upper to limit thestretch of the upper in the lateral direction. The tensile strands mayform one or more lace apertures for receiving a lace and/or may extendaround at least a portion of a lace aperture formed in the knitstructure of the knitted component.

When desirable, the article of footwear 200 or shoe 200 may also includea platform upon which the foot will rest that separates the upper 210from the foot of the person wearing the shoe. This platform is typicallya separate removable layer called an insole or sock liner (not shown)that is made of cellulose or other materials, such as thermoplastic orthermoset elastomers, including foam materials, capable of providing acushion between the ground and the foot of the person wearing the shoe200. The insole may be treated with additives to inhibit bacterialgrowth. When desirable, the insole may be incorporated with, e.g., sewninto, the upper.

Referring once again to FIGS. 4A and 4B, the outsole 220 of the shoe 200may be engaged with or attached to the upper 210 and be directly adheredthereto. However, when desirable, a portion of the outsole may beattached to the upper 210 through the use of additional meansconventionally known or used in the construction of footwear 200, suchas through the use of cements or adhesives, by mechanical connectors,and by sewing or stitching, to name a few.

When desirable, the UV radiation curable material may be used to attachtwo or more elements together. More specifically, the UV radiationcurable material may be applied to a textile or another portion of anupper and used to secure another or second layer of a material thereto.This second or additional layer may also be a textile, or it can be aninjection molded component or even a decorative element. The secondlayer may be made of a material whose composition is similar to ordifferent than the textile to which it is being attached.

The UV radiation curable material may also be used to overcoat a secondlayer that has been secured to the upper. When placed on top of thesecond layer, the UV radiation curable material may provideabrasion-resistance and/or act as a protective layer.

According to another aspect of the present disclosure, a method 400 offorming an article of footwear is provided as shown in FIG. 5 . Thismethod comprises the steps of providing 405 a molded article in the formof a molded footwear component and affixing 410 the molded componentwith an upper and optionally with other footwear components to form thearticle of footwear. As used for the purpose of this disclosure, theterm “providing” may be defined as receiving, supplying, or makingavailable something wanted or needed

The following specific examples are given to illustrate the formation ofan article or a component of an article according to the teachings ofthe present disclosure and should not be construed to limit the scope ofthe disclosure. Those skilled-in-the-art, in light of the presentdisclosure, will appreciate that many changes can be made in thespecific embodiments which are disclosed herein and still obtain alikeor similar result without departing from or exceeding the spirit orscope of the disclosure. One skilled in the art will further understandthat any properties reported herein represent properties that areroutinely measured and can be obtained by multiple different methods.The methods described herein represent one such method and other methodsmay be utilized without exceeding the scope of the present disclosure.

Example 1

This Example demonstrates the formation of an article using a moldhaving a molding surface that is transparent to UV radiation accordingto the teachings of the present disclosure. Referring now to FIG. 6 , amold 1 was designed to fit within a 7.5″ width benchtop conveyor line ofan UV curing apparatus 25. The UV curing apparatus 25 was a LC6B/LC6B-2curing unit (Heraeus Noblelight America LLC, Gaithersburg, Md.). The UVlamp 20 used in this apparatus 25 to cure the article-forming (i.e., UVradiation curable) material was a metal halide bulb. The mold 1 wasselected to have the most basic geometry, i.e., a 4″×4″ herringbone mold1 with a cavity 5 capable of being completely filled with thearticle-forming material. The mold 1 was comprised of a bulk material 10and a mold wall 15 that was formed of a cyclic olefin copolymer. Themold 1 was designed for use in a compression molding process.

A cured article 30 was formed using a paired mold 1. The mold 1 was aone-sided female mold having a mold wall 15 with a herringbonestructure. The other or opposite side was pressed against a releasepaper. One skilled in the art will understand that other surfaces, suchas a metal shim (aluminum and stainless), acrylic (PMMA) plaque, or someother flat plaque may be used as part of the mold 1 instead of releasepaper without exceeding the scope of the present disclosure. The cyclicolefin copolymer used to form the mold wall was TOPAS® Grade 6017 (TopasAdvanced Polymers Inc., Florence, Ky., USA). The mold wall 15 was formedby placing the cyclic olefin copolymer into a master molded and heateduntil cured. The cyclic olefin copolymer was processed according to themanufacturer's technical specification.

The article-forming (i.e., UV radiation curable) material was suppliedas a pre-compounded sheet. The article-forming material was an UVradiation curable polyurethane rubber (Millathane® DUV 8263, TSEIndustries Inc., Clearwater, Fla.). The UV radiation curable materialwas processed according to the manufacturer's technical specification.The material was milled to a thinner thickness, which reduced air voids.The article-forming material was placed in to the mold and compressedusing a traditional compression press (two-platen system) with theapplication of pressure above 60 psi. The temperature of the mold wasadjusted depending upon the application. In this example, thetemperature of the mold was maintained at a temperature up to about 160°C.

Referring again to FIG. 6 , after the article-forming material wascompressed in the mold 1, the combination of the mold andarticle-forming material was placed through a UV curing station asdescribed above. The resulting molded article 30 was then removed fromthe mold 1.

Example 2

This example demonstrates the formation of a component of an articleusing a mold having a molding surface that is transparent to UVradiation according to the teachings of the present disclosure.Referring now to FIG. 7A, a UV radiation curable material 33 is placedin contact with a fabric 35. In this example, the UV radiation curablematerial 33 is an UV radiation curable polyurethane rubber (Millathane®UV, TSE Industries Inc., Clearwater, Fla.) processed according to themanufacturer's technical specification. The material may be applied astwo layers 31, 33 if desirable in order to provide a variable thickness,or the second layer 31 may be of a different material. The UV radiationcurable material was pre-dried to remove surface moisture prior to use.

Referring now to FIG. 7B, the UV radiation curable material 33 andtextile 35 are placed into the mold 1. The mold 1 in this example is thesame mold 1 described above in Example 1. This mold comprises an outerbulk material 5 and a mold wall 15 having a herringbone design. In thismold at least the mold wall 15 comprises a cyclic olefin copolymer thatexhibits transparency to UV radiation.

In FIG. 7C, the mold 1 with the UV radiation curable material 33 andfabric 35 are compressed using a traditional T-shirt press with theapplication of pressure in the range of about 20 psi to about 60 psi. Inthis example, the temperature of the mold was kept below 135° C. inorder to minimize the potential for dye migration from the fabric 35.

Referring now to FIG. 7D, the compressed mold 1 was placed on a conveyerthat moved the mold 1 into alignment with a UV light source 20 as partof the UV curing apparatus 25. The resulting molded article 30 was thenremoved from the mold 1. Finally, as shown in FIG. 7E, the finishedarticle with the molded component formed therein 30 was removed from themold. As shown in FIG. 7E, the finished component of the article adheresto the fabric and incorporates the herringbone pattern of the mold.

Within this specification, embodiments have been described in a way thatenables a clear and concise specification to be written, but it isintended and will be appreciated that embodiments may be variouslycombined or separated without parting from the invention. For example,it will be appreciated that all preferred features described herein areapplicable to all aspects of the invention described herein.

The subject matter of the disclosure may also relate, among others, tothe following aspects:

-   -   1. A mold for forming a molded article, the mold comprising:        -   a mold wall comprising a cyclic olefin copolymer and having            a molding surface for contact with an article-forming            material to form the molded article.    -   2. The mold of Aspect 1, wherein the cyclic olefin copolymer        comprises a copolymer of polyethylene and norbornene.    -   3. The mold of Aspect 1 or 2, wherein the mold wall is        substantially transparent to ultraviolet (UV) light to allow the        UV light to be transmitted through the mold wall to the molding        surface.    -   4. The mold of any of Aspects 1 to 3, wherein the cyclic olefin        copolymer has a heat deflection temperature (HDT) at 0.46 MPa of        at least about 140° C. as characterized by HDT testing in        accordance with ISO 75-1 Test Standard.    -   5. The mold of Aspect 4, wherein the HDT of the cyclic olefin        copolymer is from about 165 to about 200° C.    -   6. The mold of any of Aspects 1 to 5, wherein the mold surface        has a surface energy of from about 15 to about 35 dynes/cm at        20° C. as characterized by surface measurement testing in        accordance with ISO 8296 Test Standard.    -   7. The mold of any of Aspects 1 to 6, wherein the mold wall        forms at least part of a first die portion, and the mold further        comprises a second die portion, wherein the first and second die        portions are configured to move relative to each other between        an opened position and a closed position, and wherein the first        and second die portions in the closed position defines a cavity        for molding the article-forming material.    -   8. The mold of Aspect 7, wherein the mold is a compression mold        and the first and second die portions are configured for        compression molding the article-forming material to form the        molded article.    -   9. The mold of any of Aspects 1 to 8, wherein the mold is a mold        for forming a molded footwear component, a molded apparel        component, or a molded sporting equipment component.    -   10. The mold of Aspect 9, wherein the mold is a mold for forming        a molded footwear component.    -   11. A method for making a mold for forming a molded article, the        method comprising:        -   forming a mold wall comprising a cyclic olefin copolymer and            having a molding surface for contact with an article-forming            material for forming the molded article.    -   12. The method of Aspect 11, wherein forming the mold wall        comprises:        -   introducing molten cyclic olefin copolymer to a master mold;            and        -   solidifying the molten cyclic olefin copolymer in the master            mold to form the mold wall.    -   13. The method of Aspect 11 or 12, wherein forming the mold wall        includes using an injection molding process to introduce and        solidify the molten cyclic olefin copolymer in the master mold.    -   14. The method of any of Aspects 11 to 13, wherein introducing        comprises introducing the molten cyclic olefin copolymer having        a temperature of from about 260° C. to about 320° C. to the        master mold.    -   15. The method of any of Aspects 11 to 14, wherein solidifying        comprises solidifying the molten cyclic olefin copolymer in the        master mold that has a mold temperature of from about 120 to        about 160° C.    -   16. The method of any of Aspects 11 to 15, wherein the mold is a        mold for a molded footwear component, a molded apparel        component, or a molded sporting equipment component.    -   17. The method of Aspect 16, wherein the mold is a mold for a        molded footwear component.    -   18. A method for forming a molded article, the method        comprising:        -   introducing an article-forming material to a mold that            comprises a mold wall comprising a cyclic olefin copolymer;            and        -   contacting the article-forming material with a molding            surface of the mold wall for forming the molded article.    -   19. The method of Aspect 18, wherein the cyclic olefin copolymer        comprises a copolymer of polyethylene and norbornene.    -   20. The method of Aspect 18 or 19, wherein the mold wall is        substantially transparent to ultraviolet (UV) light, and wherein        the method further comprises transmitting the UV light through        the mold wall to the molding surface for exposing the        article-forming material to the UV light.    -   21. The method of Aspect 20, wherein the article-forming        material is an UV radiation curable material, and wherein the        method further comprises curing the article-forming material in        response to exposure to the UV light.    -   22. The method of Aspect 21, wherein the UV radiation curable        material is an UV radiation curable elastomeric or rubber        material, and wherein curing comprises curing the UV radiation        curable elastomeric or rubber material in response to exposure        to the UV light.    -   23. The method of Aspect 22, wherein the UV radiation curable        elastomeric or rubber material is an UV radiation curable        polyurethane rubber, and wherein curing comprises curing the UV        radiation curable polyurethane rubber in response to exposure to        the UV light.    -   24. The method of any of Aspects 18 to 23, wherein the mold wall        forms at least part of a first die portion, and the mold further        comprises a second die portion, and wherein contacting includes        moving the first and second die portions relative to each other        to a closed position for molding the article-forming material.    -   25. The method of Aspect 24, wherein the mold is a compression        mold, and wherein contacting includes moving the first and        second die portions relative to each other to the closed        position for compression molding the article-forming material.    -   26. The method of any of Aspects 18 to 25, wherein the molded        article is a molded footwear component, a molded apparel        component, or a molded sporting equipment component.    -   27. The method of Aspect 26, wherein the molded article is a        molded footwear component.    -   28. A molded article made by any of Aspects 18 to 27.    -   29. A method of manufacturing an article of footwear, the method        comprising:        -   providing a molded article made by any of Aspects 18 to 27,            wherein the molded article is a molded footwear component;            and        -   affixing the molded footwear component and a footwear upper            and/or other footwear component to make an article of            footwear.    -   30. An apparatus for forming a molded article, the apparatus        comprising:        -   a mold comprising a mold wall that comprises a cyclic olefin            copolymer and that is substantially transparent to            ultraviolet (UV) light, wherein the mold wall has a molding            surface for contacting an article-forming material; and        -   an UV light source disposed adjacent to the mold wall on a            side opposite the molding surface and configured to generate            UV light for transmission through the mold wall to the            molding surface for exposing the article-forming material to            the UV light.    -   31. The apparatus of Aspect 30, wherein the apparatus is an        apparatus for forming a molded footwear component, a molded        apparel component, or a molded sporting equipment component.    -   32. The apparatus of Aspect 31, wherein the apparatus is an        apparatus for forming a molded footwear component.

The foregoing description of various forms of the invention has beenpresented for purposes of illustration and description. It is notintended to be exhaustive or to limit the invention to the precise formsdisclosed. Numerous modifications or variations are possible in light ofthe above teachings. The forms discussed were chosen and described toprovide the best illustration of the principles of the invention and itspractical application to thereby enable one of ordinary skill in the artto utilize the invention in various forms and with various modificationsas are suited to the particular use contemplated. All such modificationsand variations are within the scope of the invention as determined bythe appended claims when interpreted in accordance with the breadth towhich they are fairly, legally, and equitably entitled.

What is claimed is:
 1. A method for forming a molded article, the methodcomprising: contacting an article-forming material with a moldingsurface of a mold wall, wherein the molding surface comprises a cyclicolefin copolymer, and the article-forming material is an ultraviolet(UV) radiation curable polyurethane; contacting the article-formingmaterial with a first textile; while the article-forming materialremains in contact with the molding surface and the first textile,exposing the article-forming material to pressure and UV light passingthrough the molding surface; and curing the UV radiation curablepolyurethane of the molding material in response to the exposure to theUV light, thereby forming a molded component of a molded article andaffixing the first textile to the molded component.
 2. The method ofclaim 1, wherein the cyclic olefin copolymer comprises a copolymer ofpolyethylene and norbornene.
 3. The method of claim 1, wherein the moldwall is substantially transparent to UV light, and wherein the methodfurther comprises transmitting the UV light through the mold wall to themolding surface for exposing the article-forming material to the UVlight.
 4. The method of claim 1, wherein the cyclic olefin copolymer hasa heat deflection temperature (HDT) at 0.46 MPa of at least about 140°C. as characterized by HDT testing in accordance with ISO 75-1 TestStandard.
 5. The method of claim 4, wherein the HDT of the cyclic olefincopolymer is from about 165 to about 200° C.
 6. The method of claim 1,wherein the mold surface has a surface energy of from about 15 to about35 dynes/cm at 20° C. as characterized by surface measurement testing inaccordance with ISO 8296 Test Standard.
 7. The method of claim 1,wherein the mold wall forms at least part of a first die portion, andthe mold further comprises a second die portion, wherein the first andsecond die portions are configured to move relative to each otherbetween an opened position and a closed position, and wherein the firstand second die portions in the closed position define a cavity formolding the article-forming material.
 8. The method of claim 1, whereinthe mold wall forms at least part of a first die portion, and the moldfurther comprises a second die portion, and wherein contacting thearticle-forming material includes moving the first and second dieportions relative to each other to a closed position for molding thearticle-forming material.
 9. The method of claim 1, wherein the moldedarticle is a molded apparel component or a molded sporting equipmentcomponent.
 10. The method of claim 1, wherein the curing attaches thefirst textile to one or more other elements using the UV radiationmaterial.
 11. The method of claim 10, wherein a first element of the oneor more elements is a second textile.
 12. The method of claim 2, whereinthe cyclic olefin copolymer has a heat deflection temperature (HDT) at0.46 MPa of at least about 140° C. as characterized by HDT testing inaccordance with ISO 75-1 Test Standard.
 13. The method of claim 12,wherein the HDT of the cyclic olefin copolymer is from about 165 toabout 200° C.
 14. The method of claim 13, wherein the molding surfacehas a surface energy of from about 15 to about 35 dynes/cm at 20° C. ascharacterized by surface measurement testing in accordance with ISO 8296Test Standard.
 15. A method of manufacturing an article, the methodcomprising: forming a molded article in accordance with the method ofclaim 1; and affixing the molded article and a part of a component ofthe article to make an article.
 16. The method of claim 15, wherein thecuring attaches two or more elements together using the UV curablematerial.
 17. The method of claim 16, wherein a first element of the twoor more elements is a second textile.
 18. The method of claim 17,wherein a second of the two or more elements is part of anothercomponent of the article, and wherein the curing attaches the secondtextile to the other component.
 19. The method of claim 1, wherein themolded article is a molded apparel component or a molded sportingequipment component.